Process of preparing ethyl benzene



May 29, l945- c. N. -KIMBERLIN JR 2,377,243

PROCESS OF PREPARING ETHYL BENZENE Filed D ec. 5I, 1941 T 2 A/o mais;

,woLYA/KYL .zagzzlva-r/vzs Merkur l /a' gf". l Ml' ethyl benzenes and higher constituents.

Patentedl May 29, 1945 UNITED s'ln'ri-:s` PATENT oFFlcl-z PROCESS F PREPABING ETHYL BEZENE Charles'N. Kimberlin, Jr., Baton Rouge, La., as-

msignor to Standard Oil Development Company,

`a corporation of Delaware applicati@ December 31, 1941, serial No.. 425,055 1' claim. i (cl. 26o-671) ethylene under suitable conditions and in the presence of a'Friedel-Crafts type catalyst. These reactions are generally conducted at a temperature in the range from about 125 F. to about 250" F. Conventional operating temperatures are in the range from about 160 F.`to about l200" F. The catalyst employed usually comprises a metallic halide such as aluminum chloride, zinc chloride, or iron chloride. Hydrogen chloride or alkyl halides are sometimes added as promoters. However, in these reactions, particularly in operations conducted for the production of monoethyl benzene, itis relativelydifcult to. control the course of the reaction so that a relatively high yield'of monoethyl benzene is secured rather than poly- One method which has been found to increase the yield of monoethyl benzene as compared to poly-Y ethyl benzenes is to separate the polyethyl benzenes from the products of reactionand recycle them to the reaction zone. It is likewise difiicult to react all of the benzene and also to recover all of the unreacted benzene from the escaping gases. While it Would be desirable in many respects to use ethylene gas of comparatively high purity for the reaction, ordinarily such a gas is not readily available for commercial operations and ethylene diluted with large amounts oi ethane as well as smaller amounts of other unreactive gases is used. These gases which dilute the ethylene pass through the reaction unchanged and are generally vented from the system for use as fuel or any other suitable purpose. The temperature of the reaction is ordinarily higher than the temperature at which the gases are discharged from the system so they are saturated with benzene vapor. The amount of benzene lost in this manner represents an appreciable proportion of the total benzene feed.

A typical ethylene gas available commercially contains approximately 38% ethylene and approximately 62% ethane. Thus when 100 mols of benzene are treated with 37 mols of ethylene to produce ethyl benzene under suitable reaction conditions, the ethylene is diluted with approximately 60 mols of ethane. When 90% of the ethylene is converted to ethyl benzene or other products of the reaction, the outlet gas contains the 60 mols of` ethane together with about 4 mols of unreacted ethylene.` When this gas is separated from the products of reaction at 30 C., it contains about 11% of the benzene feed. If the temperature of the separation is decreased to C., the amount 0f benzene lost is 6% and even at the freezing point of benzene approximately 3% will be lost in the waste gases.

\ An object of this invention is to provide amethod of recovering the benzene that is expelled from the reaction vessel with the unreacted hydrocarbon gases. A

'I'he process of this invention will be readily understood by referring to the attached drawing illustrating the embodiments of the same.

Referring to the drawing, the feed material, comprising olenic and aromatic constituents, is introduced into reaction zone l comprising a packed tower by means of line '2. Fresh catalyst, which for the purpose of description is taken to be aluminum chloride, is introduced into reaction zone I by means of line 3. Intimate mixing between the catalyst and the feed constituents is secured by means of the packed tower. The temperature and pressure conditions within reaction zone I are maintained to secure maximum yield of the desired product. The reaction products together vwith the catalyst overflow by means of conduit 5 into settling zone 6. Unreacted gases are removed overhead from settling zone 8 by means of line 1, while the catalyst which separates, isremoved from the bottom of the zone E by means of line 8. This catalyst may be recycled to zone I by means of line 9 or withdrawn from the system by means of line I0. The reaction products are passed to product receiving zone II by means of line I2 and then introduced into distillation zone I3 by means of line I4.

vTemperature and pressure conditions in distillation zone I3fare adjusted to remove overhead by means of line I9 unreacted aromatic constituents which are preferably recycled to zone I with the fresh feed. The alkylated aromatics are withdrawn from zone I3 by means of line I5 and of line i1 and any polyethyl benzenes formed by means ofy line I8. A part of the polyethyl benzenes mayl be discharged from the system through iinel'.

.The unreacted gases'removed by means oi' line l contain substantial amounts of benzene vapors. To recover this benzene the gases are passed t0 packed tower 26 into the upper part o! which polyethyl benzenes are introduced by means of line 20. The polyethyl benzenes are obtained from line I8 by means oi line 2l. The benzene is absorbed from the gases by the polyethyl benzenes in the packed tower 25. The unreacted gases from which the benzene has been absorbed are r removed from the packed tower 25 by means of line 22 and vented from the system. Thepolyethyl benzenes with the recovered benzene in solution are passed from the lower part oi the tower through line 23 to line i9 and then recycled to the reaction zone l.

Since the polyethyl benzenes produced in the reaction have a comparatively low vapor pressure` they constitute an excellent solvent for evident that the use oi these by-products as an absorption medium for the benzene in the unreacted gases is particularly advantageous in that it eliminates a separation step which would be required if an absorption medium were used which could not be recycled to the reaction zone.

It is not intended to limit this invention to the recovery of benzene in the particular reaction or ethylene and benzene as the process is also suitable for use in the production of practically 4any alkylated benzene.

I claim:

A process for alkylating aromatica which comprises passing a reed material containing bene zene. ethylene and ethane into the bottom or a re action zone in which a body of catalyst is maintained at a temperature of about 160 F. to alkylate the benzene, adapting operating conditions so that unreacted constituents, reaction products and catalyst overow to a settling sone wherein unreacted gaseous constituents saturated with benzene vapors separate from the reaction products and the catalyst, recovering monethyl benzene and polvethyl benzenes from the prodf uctsof reaction, scrubbing the unreacted vaporized constituents with the polyethyl benzenes, separating the polyethyl benzenes with benzene insolutionL from gaseous reaction products and recycling the solution oi benzene in polyethyl ben= 30 zenes to the reaction zone.

CHARLES N. KIIVIBERLIN. Jil. 

